EP0146560B1 - Process for preparing polyanilines and their applications to electrochemical generators - Google Patents

Process for preparing polyanilines and their applications to electrochemical generators Download PDF

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EP0146560B1
EP0146560B1 EP84901780A EP84901780A EP0146560B1 EP 0146560 B1 EP0146560 B1 EP 0146560B1 EP 84901780 A EP84901780 A EP 84901780A EP 84901780 A EP84901780 A EP 84901780A EP 0146560 B1 EP0146560 B1 EP 0146560B1
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Prior art keywords
process according
chosen
oxidation
polyanilines
liquid phase
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German (de)
French (fr)
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EP0146560A1 (en
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Eugène "La Biollette" GENIES
Gérard Pierre
Christian Santier
Constantin Tsintavis
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a process for preparing polyanilines used in particular as the electrode material of an electrochemical generator.
  • polyanilines polymers originating from the condensation of the aniline itself, but also of that of its derivatives.
  • polyanilines can be prepared by electrochemical polymerization as described in Chemical Abstracts, Vol. 93, 1980, No. 168925 z and in Chemical Abstracts, Vol. 94, 1981, n ° 84917f. They can also be prepared by chemical oxidation in a sulfuric medium using ammonium persulfate as described in the Bulletin de la cios Chimique de France, 1972, No. 11, pages 4083-4084.
  • these methods of preparation have poor yields and lead to compounds containing many ill-defined oligomers. This results in a dispersion of the electrochemical properties and therefore of the qualities of the batteries produced from the latter.
  • the present invention therefore provides a process for the preparation of polyanilines having yields close to the theory and without the formation of oligomeric side products, suitable for use as electrode active material in a battery and having better electrochemical properties.
  • the subject of the invention is a process for preparing polyanilines by oxidation of a compound chosen from aniline, para-aminodiphenyl amine and their derivatives, characterized in that this oxidation is carried out in the liquid phase in a superacid having a pH equivalent of less than 0 with respect to water, comprising fluoride ions at a concentration of 0.5 to 10 ions.g / 1.
  • the term “superacid” means any acid mixture whose pH equivalent is less than 0 with reference to water, such as for example sulfuric acid, phosphoric acid, hydrofluoric acid, benzene sulfonic acid, etc.
  • the concentration of the liquid phase in the compound chosen from aniline, paraminodiphenyl amine and their derivatives is between 10- 3 and 4 mol / 1.
  • the liquid phase containing the superacid and the fluoride ions consists of the eutectic NH 3 , HF which contains approximately 54.2% of free HF and 80.9% of total HF (in weight).
  • the concentration of fluoride ions in the liquid phase is 0.5 to 10 ions.g / l.
  • the liquid phase can be an aqueous or organic solution containing the super acid and the fluoride ions.
  • an anilinium fluoride solution is obtained, the concentration of which can vary between 10- 3 and 4 mol / 1.
  • the chemical route involves mixing the preceding solution with a solution in the same super acid of oxidizing agents such as potassium dichromate, potassium permanganate, osmium tetroxide and ammonium persulfate.
  • oxidizing agents such as potassium dichromate, potassium permanganate, osmium tetroxide and ammonium persulfate.
  • the concentration of aniline in para-aminodiphenyl amine or in an aniline or paraminodiphenyl amine derivative of the super-acid solution is such that in the final liquid phase, there is a concentration of 10- 3 to 4 mol / 1 of aniline, paraminodiphenyl amine or one of their derivatives.
  • the concentration of oxidizing agent in the solution added to the solution of aniline, para-aminodiphenyl amine or their derivatives is such that a concentration of oxidizing agent of 10- 3 is obtained in the final liquid phase. at 4 mol / 1.
  • the polyanilines are electrolytically deposited on a support such as platinum, nickel, "Monel", carbon or any support made of material coated with carbon, for example a support made of stainless steel coated with a graphite paint. .
  • the current densities used for this deposit vary between 0.05 and 100 mA / cm 2 , the formation of polyanilines is quantitative.
  • the battery electrode is thus obtained directly; the polyanilines prepared according to this second embodiment are very stable and adhere very strongly to the support (grid or plate).
  • the polyanilines prepared according to the process of the invention have electrochemical properties much superior to the other conductive conjugate polymers. Thus, after 1,600 complete charge and discharge cycles, the polyaniline-based battery prepared according to the invention still retains 80% of its capacity, while other polymers, for example polypyrrole, lose 20% of their capacity after 100 cycles.
  • the active material of the positive electrode is a polyaniline
  • the active material of the negative electrode can be constituted by a reactive metal such as lithium, by a conductive conjugate polymer, by carbon or by a composite material, such as a ceramic (tin oxide, indium oxide, titanium oxide doped with fluorine or antimony).
  • a reactive metal such as lithium and lithium-aluminum alloys are used.
  • the electrolytes, associated with the electrodes described above, used for producing a generator using a polyaniline prepared according to the invention, are preferably lithium salts such as perchlorate, perborate and hexafluorophosphate.
  • lithium salts such as perchlorate, perborate and hexafluorophosphate.
  • the electrolytes are dissolved in a solvent such as linear ethers (for example dimethoxyethane), cyclic ethers (for example dioxolane or tetramethylhydrofuran) or esters (for example propylene carbonate).
  • electrolytes or the solvents can be used alone or as a mixture.
  • the electrolyte concentrations in the solvent depend on the choice of each; in the case of lithium perchlorate and propylene carbonate the concentration of the salt in the solvent is 1 to 3 mol / l.
  • an electrochemical generator comprises a sealed and insulating housing 1, containing an electrolyte 2.
  • a first current collector 3 covered with a positive active material 5 and a collector 7 in contact with a negative active material 9.
  • Separators 11 and 13 can be provided to avoid any short-circuits.
  • generators or unit electrochemical batteries can be used for mounting in series or in parallel.
  • the polyethylene casing comprises a first collector 3 made of "Monel” covered with a layer of polyaniline 5 approximately 100 ⁇ m thick obtained under the following conditions:
  • separator 11 and / or 13 other ion exchange membranes, microporous teflon®, paper, glass wool, polymer membranes, for example polyethylene, polypropylene, etc.
  • the housing is then filled with an electrolyte formed from a molar solution of lithium perchlorate in propylene carbonate, then closed.
  • the generator thus produced has an electromotive force of 3.5 volts with a current density of approximately 10 mA per cm 2 .
  • the collectors 3 and 7 are in the form of a grid or a plate.
  • FIG. 2 shows two cyclic voltammetry curves produced with a scanning speed of 0.1 Vs- 1 of an electrode covered with 0.1 ⁇ m of polyaniline in acetonitrile containing 0.1 M of perchlorate of lithium.
  • the registration of these curves is effected by means of a PAR 173 potentiostat, the potential being controlled with respect to a reference electrode Ag / Ag + 10- 2 M.
  • the curves A and B are those obtained after 10 and respectively 1,600 scans. It can be seen, on examining these curves, that the electrical characteristics are little altered by the number of scans.
  • FIG. 3 the discharge curve of a polyaniline / lithium generator at a constant intensity of 30 ⁇ A is shown, the positive electrode having a surface of 1 cm 2 and being covered with a layer of polyaniline of approximately 2 ⁇ m.
  • An electrochemical generator is produced in the same way as above, comprising polyaniline as active material for the positive electrode and a lithium-aluminum alloy as material for the negative electrode.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The process comprises the oxidation of a compound selected among aniline, para-aminodiphenylamine and derivatives thereof, in a super acid, in liquid phase, comprising fluoride ions for example in the eutectic NH3, HF, either by chemical process by means of an oxidation agent or by electrochemical process. The polyanilines obtained may be used as positive electrode material (5) in an electrochemical generator having two current collectors (3 and 9) and a negative electrode material (9) consisting for example of lithium or lithium-aluminium alloy.

Description

La présente invention a pour objet un procédé de préparation de polyanilines employées notamment comme matière d'électrode d'un générateur électrochimique.The present invention relates to a process for preparing polyanilines used in particular as the electrode material of an electrochemical generator.

Selon l'invention, par polyanilines, il faut entendre les polymères provenant de la condensation de l'aniline elle-même, mais aussi de celle de ses dérivés.According to the invention, by polyanilines is meant polymers originating from the condensation of the aniline itself, but also of that of its derivatives.

On sait que les polyanilines sont utilisées pour la réalisation de batterie électrochimique (voir par exemple le brevet français 1 519 729 et Chemical Abstracts, vol. 77,1972, n° 6298q).It is known that polyanilines are used for the production of an electrochemical battery (see for example French patent 1,519,729 and Chemical Abstracts, vol. 77,1972, n ° 6298q).

Ces polyanilines peuvent être préparées par polymérisation électrochimique comme il est décrit dans Chemical Abstracts, Vol. 93, 1980, n° 168925 z et dans Chemical Abstracts, Vol. 94, 1981, n° 84917f. On peut aussi les préparer par oxydation chimique en milieu sulfurique au moyen de persulfate d'ammonium comme il est décrit dans le Bulletin de la Société Chimique de France, 1972, n° 11, pages 4083-4084. Cependant, ces modes de préparation ont de mauvais rendements et conduisent à des composés contenant de nombreux oligomères mal définis. Cela se traduit par une dispersion des propriétés électrochimiques et donc des qualités des batteries réalisées à partir de ces dernières.These polyanilines can be prepared by electrochemical polymerization as described in Chemical Abstracts, Vol. 93, 1980, No. 168925 z and in Chemical Abstracts, Vol. 94, 1981, n ° 84917f. They can also be prepared by chemical oxidation in a sulfuric medium using ammonium persulfate as described in the Bulletin de la Société Chimique de France, 1972, No. 11, pages 4083-4084. However, these methods of preparation have poor yields and lead to compounds containing many ill-defined oligomers. This results in a dispersion of the electrochemical properties and therefore of the qualities of the batteries produced from the latter.

La présente invention propose donc un procédé de préparation de polyanilines ayant des rendements proches de la théorie et sans formation de produits secondaires oligomères, aptes à être utilisées comme matière active d'électrode dans une batterie et ayant de meilleures propriétés électrochimiques.The present invention therefore provides a process for the preparation of polyanilines having yields close to the theory and without the formation of oligomeric side products, suitable for use as electrode active material in a battery and having better electrochemical properties.

Plus précisément, l'invention a pour objet un procédé de préparation de polyanilines par oxydation d'un composé choisi parmi l'aniline, la para-aminodiphényl amine et leurs dérivés, caractérisé en ce que l'on réalise cette oxydation en phase liquide dans un superacide ayant un équivalent pH inférieur à 0 par rapport à l'eau, comportant des ions fluorure à une concentration de 0,5 à 10 ions.g/1.More specifically, the subject of the invention is a process for preparing polyanilines by oxidation of a compound chosen from aniline, para-aminodiphenyl amine and their derivatives, characterized in that this oxidation is carried out in the liquid phase in a superacid having a pH equivalent of less than 0 with respect to water, comprising fluoride ions at a concentration of 0.5 to 10 ions.g / 1.

Par superacide, on entend tous mélanges acides dont l'équivalent pH est inférieur à 0 par référence à l'eau, comme par exemple l'acide sulfurique, l'acide phosphorique, l'acide fluorhydrique, l'acide benzène sulfonique...The term “superacid” means any acid mixture whose pH equivalent is less than 0 with reference to water, such as for example sulfuric acid, phosphoric acid, hydrofluoric acid, benzene sulfonic acid, etc.

Selon une caractéristique secondaire de l'invention, la concentration de la phase liquide en composé choisi parmi l'aniline, la paraminodiphényl amine et leurs dérivés est comprise entre 10-3 et 4 mol/1.According to a secondary characteristic of the invention, the concentration of the liquid phase in the compound chosen from aniline, paraminodiphenyl amine and their derivatives is between 10- 3 and 4 mol / 1.

Selon une autre caractéristique secondaire de l'invention, la phase liquide contenant le superacide et les ions fluorure est constituée par l'eutectique NH3, HF qui contient environ 54,2 % de HF libre et 80,9 % de HF total (en poids).According to another secondary characteristic of the invention, the liquid phase containing the superacid and the fluoride ions consists of the eutectic NH 3 , HF which contains approximately 54.2% of free HF and 80.9% of total HF (in weight).

On peut aussi utiliser des mélanges RNH2, HF avec R représentant un radical alkyle et des mélanges pyridine, HF.It is also possible to use mixtures RNH 2 , HF with R representing an alkyl radical and mixtures of pyridine, HF.

Selon une autre caractéristique secondaire de l'invention, la concentration en ions fluorure de la phase liquide est de 0,5 à 10 ions.g/l.According to another secondary characteristic of the invention, the concentration of fluoride ions in the liquid phase is 0.5 to 10 ions.g / l.

La phase liquide peut être une solution aqueuse ou organique contenant le super acide et les ions fluorure.The liquid phase can be an aqueous or organic solution containing the super acid and the fluoride ions.

Par mélange de l'aniline ou de ses dérivés et du super acide contenant des ions fluorure, on obtient une solution de fluorure d'anilinium dont la concentration peut varier entre 10-3 et 4 mol/1.By mixing the aniline or its derivatives and the super acid containing fluoride ions, an anilinium fluoride solution is obtained, the concentration of which can vary between 10- 3 and 4 mol / 1.

Les modes de préparation des polyanilines asont les suivants:

  • - dans un premier temps, on réalise un mélange de l'aniline, de la para-aminodiphényl amine ou l'un de leurs dérivés et de la solution super acide contenant des ions fluorure;
  • - dans un deuxième temps, on réalise l'oxydation en polyanilines soit par voie chimique, soit par voie électrochimique.
The polyaniline preparation methods are as follows:
  • - Firstly, a mixture of aniline, para-aminodiphenyl amine or one of their derivatives and of the super acid solution containing fluoride ions is produced;
  • - Secondly, the oxidation to polyanilines is carried out either chemically or electrochemically.

La voie chimique fait intervenir le mélange de la solution précédente avec une solution dans le même super acide d'agents oxydants tel que le bichromate de potassium, le permanganate de potassium, le tétroxyde d'osmium et le persulfate d'ammonium.The chemical route involves mixing the preceding solution with a solution in the same super acid of oxidizing agents such as potassium dichromate, potassium permanganate, osmium tetroxide and ammonium persulfate.

Lorsque l'on réalise l'oxydation par voie chimique la concentration en aniline en para-aminodiphényl amine ou en dérivé d'aniline ou de paraminodiphényl amine de la solution super-acide est telle que dans la phase liquide finale, on ait une concentration de 10-3 à 4 mol/1 d'aniline, de paraminodiphényl amine ou d'un de leurs dérivés. De même, la concentration en agent oxydant de la solution ajoutée à la solution d'aniline, de para-aminodiphényl amine ou de leurs dérivés, est telle que l'on obtienne dans la phase liquide finale une concentration en agent oxydant de 10-3 à 4 mol/1.When the chemical oxidation is carried out, the concentration of aniline in para-aminodiphenyl amine or in an aniline or paraminodiphenyl amine derivative of the super-acid solution is such that in the final liquid phase, there is a concentration of 10- 3 to 4 mol / 1 of aniline, paraminodiphenyl amine or one of their derivatives. Similarly, the concentration of oxidizing agent in the solution added to the solution of aniline, para-aminodiphenyl amine or their derivatives, is such that a concentration of oxidizing agent of 10- 3 is obtained in the final liquid phase. at 4 mol / 1.

Par voie électrochimique, les polyanilines sont déposées électrolytiquement sur un support tel que le platine, le nickel, le "Monel", le carbone ou tout support en matériau revêtu de carbone, par exemple un support en acier inoxydable revêtu d'une peinture au graphite. Les densités de courant utilisées pour ce dépôt varient entre 0,05 et 100 mA/cm2, la formation des polyanilines est quantitative. On obtient ainsi directement l'électrode de la batterie; les polyanilines préparées selon ce second mode de réalisation sont très stables et adhèrent très fortement au support (grille ou plaque).Electrochemically, the polyanilines are electrolytically deposited on a support such as platinum, nickel, "Monel", carbon or any support made of material coated with carbon, for example a support made of stainless steel coated with a graphite paint. . The current densities used for this deposit vary between 0.05 and 100 mA / cm 2 , the formation of polyanilines is quantitative. The battery electrode is thus obtained directly; the polyanilines prepared according to this second embodiment are very stable and adhere very strongly to the support (grid or plate).

Les polyanilines préparées selon le procédé de l'invention possèdent des propriétés électrochimiques très supérieures aux autres polymères conjugués conducteurs. Ainsi, après 1 600 cycles de charge et décharge complètes, la batterie à base de polyanilines préparées selon l'invention conserve encore 80 % de sa capacité, alors que d'autres polymères, le polypyrrole par exemple, perdent 20 % de leur capacité après 100 cycles.The polyanilines prepared according to the process of the invention have electrochemical properties much superior to the other conductive conjugate polymers. Thus, after 1,600 complete charge and discharge cycles, the polyaniline-based battery prepared according to the invention still retains 80% of its capacity, while other polymers, for example polypyrrole, lose 20% of their capacity after 100 cycles.

Les composés utilisables pour la mise en oeuvre du procédé de l'invention, répondent à la formule générale suivante:

Figure imgb0001
dans laquelle R1, R2, R3, R4, R5, R6, R7, R8 et Rg qui peuvent être identiques ou différents, représentent un atome d'hydrogène, un radical aryle ou alkyle, un groupement choisi parmi NO2, NH2, CF3, S02, CN, OCH3, Cl , F,
Figure imgb0002
Figure imgb0003
SR (avec R = radical alkyle aryle) ou un radical choisi parmi les radicaux alkyles et aryles comportant éventuellement un ou plusieurs substituants choisis dans le groupe comprenant N02, NH2. CF3, S02, CN, OCH3, Cl, F, SCN, OCN,
Figure imgb0004
Figure imgb0005
SR (avec R - radical alkyle, aryle).The compounds which can be used for carrying out the process of the invention correspond to the following general formula:
Figure imgb0001
 in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and Rg which may be identical or different, represent a hydrogen atom, an aryl or alkyl radical, a chosen group among NO 2 , NH 2 , CF 3 , S0 2 , CN, OCH 3 , Cl, F,
Figure imgb0002
Figure imgb0003
 SR (with R = aryl alkyl radical) or a radical chosen from alkyl and aryl radicals optionally comprising one or more substituents chosen from the group comprising NO 2 , NH 2 . CF 3 , S0 2 , CN, OCH 3 , Cl, F, SCN, OCN,
Figure imgb0004
Figure imgb0005
 SR (with R - alkyl, aryl radical).

Lorsque la matière active d'électrode positive est une polyaniline, la matière active de l'électrode négative peut être constituée par un métal réactif tel que le lithium, par un polymère conjugué conducteur, par du carbone ou par un matériau composite, comme une céramique (oxyde d'ètain, oxyde d'indium, oxyde de titane dopé au fluor ou à l'antimoine). De préférence, on utilise un métal réactif tel que le lithium et les alliages lithium-aluminium.When the active material of the positive electrode is a polyaniline, the active material of the negative electrode can be constituted by a reactive metal such as lithium, by a conductive conjugate polymer, by carbon or by a composite material, such as a ceramic (tin oxide, indium oxide, titanium oxide doped with fluorine or antimony). Preferably, a reactive metal such as lithium and lithium-aluminum alloys are used.

Les électrolytes, associés aux électrodes décrites ci-dessus, employés pour la réalisation d'un générateur utilisant une polyaniline préparée selon l'invention, sont de préférence des sels de lithium tels que le perchlorate, le perborate et l'hexafluorophosphate. Néanmoins, on pourrait employer l'hexafluorophosphate de sodium, le fluoborate de tétraméthylammonium, le chlorure de tétraméthylammonium, le fluorure de tétraéthylammonium ou de tétrabutylammonium. Les électrolytes sont dissous dans un solvant tel que les éthers linéaires (diméthoxyéthane, par exemple), des éthers cycliques (dioxolane ou tétraméthylhydrofurane, par exemple) ou des esters (carbonate de propylène, par exemple).The electrolytes, associated with the electrodes described above, used for producing a generator using a polyaniline prepared according to the invention, are preferably lithium salts such as perchlorate, perborate and hexafluorophosphate. However, one could use sodium hexafluorophosphate, tetramethylammonium fluoborate, tetramethylammonium chloride, tetraethylammonium or tetrabutylammonium fluoride. The electrolytes are dissolved in a solvent such as linear ethers (for example dimethoxyethane), cyclic ethers (for example dioxolane or tetramethylhydrofuran) or esters (for example propylene carbonate).

Bien évidemment, les électrolytes ou les solvants peuvent être utilisés seuls ou en mélange.Obviously, the electrolytes or the solvents can be used alone or as a mixture.

Les concentrations en électrolyte dans le solvant dépendent du choix de chacun; dans le cas de perchlorate de lithium et du carbonate de propylène la concentration du sel dans le solvant est de 1 à 3 mol/I.The electrolyte concentrations in the solvent depend on the choice of each; in the case of lithium perchlorate and propylene carbonate the concentration of the salt in the solvent is 1 to 3 mol / l.

En se référant aux dessins annexés, d'autres avantages et caractéristiques de la présente invention apparaîtront mieux à la lecture de la description ci-après, donnée à titre illustratif et non limitatif.

  • La figure 1 représente, en coupe, un générateur comprenant une électrode chargée de polyaniline.
  • La figure 2 représente les courbes de voltamétrie cyclique de la polyaniline.
  • La figure 3 représente la courbe de décharge d'un générateur à intensité constante.
With reference to the accompanying drawings, other advantages and characteristics of the present invention will appear better on reading the description below, given by way of illustration and not limitation.
  • FIG. 1 represents, in section, a generator comprising an electrode charged with polyaniline.
  • FIG. 2 represents the cyclic voltammetry curves of the polyaniline.
  • Figure 3 shows the discharge curve of a constant current generator.

En se référant à la figure 1, on rappelle qu'un générateur électrochimique comporte un boîtier étanche et isolant 1, contenant un électrolyte 2. Dans ce boîtier sont placés un premier collecteur de courant 3 recouvert d'une matière active positive 5 et un collecteur 7 en contact avec une matière active négative 9. Des séparateurs 11 et 13 peuvent être prévus pour éviter tous courts-circuits. Bien entendu, plusieurs générateurs ou batteries électrochimiques unitaires peuvent servir à réaliser un montage en série ou en parallèle.Referring to Figure 1, it is recalled that an electrochemical generator comprises a sealed and insulating housing 1, containing an electrolyte 2. In this housing are placed a first current collector 3 covered with a positive active material 5 and a collector 7 in contact with a negative active material 9. Separators 11 and 13 can be provided to avoid any short-circuits. Of course, several generators or unit electrochemical batteries can be used for mounting in series or in parallel.

Sur la figure 1, le boîtier en polyéthylène comporte un premier collecteur 3 en "Monel" recouvert d'une couche de polyaniline 5 d'environ 100 µm d'épaisseur obtenue dans les conditions suivantes:In FIG. 1, the polyethylene casing comprises a first collector 3 made of "Monel" covered with a layer of polyaniline 5 approximately 100 μm thick obtained under the following conditions:

. Dans un réacteur, on introduit 50 cm3 de super acide constitué par l'eutectique NH3, HF auquel on ajoute 0,5 cm3 d'aniline.. 50 cm 3 of super acid consisting of the eutectic NH 3 , HF are added to a reactor, to which 0.5 cm 3 of aniline is added.

. Dans le bain obtenu, on place une électrode en "Monel" de 40 cm2 en face d'une electrode de nickel et on applique un courant constant de 1 mA/cm2 pendant une heure. L'anode en "Monel" devenue noir intense par suite du dépôt de 60 mg de polyaniline est lavée à l'eau, à l'acétone, puis au carbonate de propylène.. In the bath obtained, a 40 cm2 "Monel" electrode is placed in front of a nickel electrode and a constant current of 1 mA / cm 2 is applied for one hour. The "Monel" anode which has become intense black as a result of the deposition of 60 mg of polyaniline is washed with water, with acetone, then with propylene carbonate.

. On place ensuite dans le boîtier 1 une membrane en Nafion (0) 11 et un tissu en fibres minérales 13 et enfin un deuxième collecteur en acier inoxydable 7 sur lequel est déposée, par électrolyse, une couche de lithium 9 jouant le rôle de matière active négative. On peut aussi utiliser comme séparateur 11 et/ou 13 d'autres membranes échangeuses d'ions, du téflon® microporeux, du papier, de la laine de verre, des membranes en polymères, par exemple en polyéthylène, polypropylène, etc.. Then placed in the housing 1 a Nafion membrane ( 0 ) 11 and a mineral fiber fabric 13 and finally a second stainless steel collector 7 on which is deposited, by electrolysis, a layer of lithium 9 playing the role of active material negative. It is also possible to use as separator 11 and / or 13 other ion exchange membranes, microporous teflon®, paper, glass wool, polymer membranes, for example polyethylene, polypropylene, etc.

. Le boîtier est ensuite rempli d'un électrolyte formé d'une solution molaire de perchlorate de lithium dans du carbonate de propylène, puis obturé. Le générateur ainsi réalisé présente une force électromotrice de 3,5 volts avec une densité de courant d'environ 10 mA par cm2.. The housing is then filled with an electrolyte formed from a molar solution of lithium perchlorate in propylene carbonate, then closed. The generator thus produced has an electromotive force of 3.5 volts with a current density of approximately 10 mA per cm 2 .

Les collecteurs 3 et 7 se présentent sous forme de grille ou de plaque.The collectors 3 and 7 are in the form of a grid or a plate.

Sur la figure 2, on a représenté deux courbes de voltamétrie cyclique réalisées avec une vitesse de balayage de 0,1 Vs-1 d'une électrode recouverte de 0,1 µm de polyaniline dans l'acétonitrile contenant 0,1 M de perchlorate de lithium.FIG. 2 shows two cyclic voltammetry curves produced with a scanning speed of 0.1 Vs- 1 of an electrode covered with 0.1 μm of polyaniline in acetonitrile containing 0.1 M of perchlorate of lithium.

L'enregistrement de ces courbes s'est fait au moyen d'un potentiostat PAR 173, les potentiels étant contrôlés par rapport à une électrode de référence Ag/Ag+ 10-2 M. Les courbes A et B sont celles obtenues respectivement après 10 et 1 600 balayages. On constate, à l'examen de ces courbes, que les caractéristiques électriques sont peu altérées par le nombre de balayages.The registration of these curves is effected by means of a PAR 173 potentiostat, the potential being controlled with respect to a reference electrode Ag / Ag + 10- 2 M. The curves A and B are those obtained after 10 and respectively 1,600 scans. It can be seen, on examining these curves, that the electrical characteristics are little altered by the number of scans.

Enfin sur la figure 3, on a représenté la courbe de décharge d'un générateur polyaniline/lithium à intensité constante de 30 µA, l'électrode positive ayant une surface de 1 cm2 et étant recouverte d'une couche de polyaniline d'environ 2 µm.Finally in FIG. 3, the discharge curve of a polyaniline / lithium generator at a constant intensity of 30 μA is shown, the positive electrode having a surface of 1 cm 2 and being covered with a layer of polyaniline of approximately 2 µm.

On réalise de la même façon que précédemment un générateur électrochimique comportant de la polyaniline comme matière active d'électrode positive et un alliage lithium-aluminium comme matière d'électrode négative.An electrochemical generator is produced in the same way as above, comprising polyaniline as active material for the positive electrode and a lithium-aluminum alloy as material for the negative electrode.

Le dépôt de la polyaniline est effectué par voie électrochimique, dans les mêmes conditions que précédemment, en utilisant 14 000 C pour déposer la polyaniline sur un support en graphite de 448 cm2 de surface. On utilise comme électrolyte 250 cm3 de carbonate de propylène contenant 1 mol/1 de LiC104. Les caractéristiques du générateur ainsi obtenu sont les suivantes:

  • - capacité: 2 700 C,
  • - cyclage: 25 cycles à 80 % de profondeur,
  • - courants de cyclages: 500, 1000, 2000 µA/cm2,
  • - courant maximum: 4,5 A,
  • - capacité massique: 126 Ah/kg,
  • - autodécharge: 2,6 mV/h,
  • - tension: 3,4 V,
  • - résistance interne: 0,26 Ω.
The deposition of the polyaniline is carried out electrochemically, under the same conditions as above, using 14,000 ° C. to deposit the polyaniline on a graphite support with a surface area of 448 cm 2 . 250 cm 3 of propylene carbonate containing 1 mol / 1 of LiC10 4 is used as the electrolyte. The characteristics of the generator thus obtained are as follows:
  • - capacity: 2,700 C,
  • - cycling: 25 cycles at 80% depth,
  • - cycling currents: 500, 1000, 2000 µA / cm 2 ,
  • - maximum current: 4.5 A,
  • - mass capacity: 126 Ah / kg,
  • - self-discharge: 2.6 mV / h,
  • - voltage: 3.4 V,
  • - internal resistance: 0.26 Ω.

Avec un autre générateur électrochimique ayant comme matière active d'électrode positive de la polyaniline obtenue par le procédé de l'invention, comme matière active d'électrode négative un alliage lithium-aluminium et comme électrolyte du carbonate de propylène contenant 1 mol/1 de LiC104, on a obtenu les résultats suivants:

  • - capacité massique: 140 Ah/kg,
  • - capacité maximum à la décharge: 15 C/cm2,
  • - courant de court-circuit: 18 mA/cm2,
  • - cyclages: 100 µA durant 45 h,
    • 0,5 mA durant 8 h 30,
      • 1 mA durant 4 h,
      • 2 mA durant 1 h 40,
  • - tension: 3,2 à 3,4 V,
  • - autodécharge: 1 à 2 mV/h avec séparateur,
    • 20 mV/h sans séparateur.
With another electrochemical generator having as active material of positive electrode polyaniline obtained by the process of the invention, as active material of negative electrode a lithium-aluminum alloy and as electrolyte of propylene carbonate containing 1 mol / 1 of LiC10 4 , the following results were obtained:
  • - mass capacity: 140 Ah / kg,
  • - maximum capacity at discharge: 15 C / cm 2 ,
  • - short-circuit current: 18 mA / cm 2 ,
  • - cycling: 100 µA for 45 h,
    • 0.5 mA for 8 h 30,
      • 1 mA for 4 h,
      • 2 mA for 1 h 40,
  • - voltage: 3.2 to 3.4 V,
  • - self-discharge: 1 to 2 mV / h with separator,
    • 20 mV / h without separator.

Claims (9)

1. Process for the preparation of polyanilines by oxidation of a compound chosen from among anilines, para-aminodiphenylamine and their derivatives, characterized in that this oxidation is performed in the liquid phase in a super acid having an equivalent pH below 0 with respect to water containing fluoride ions with a concentration of 0.5 to 10 ions. g/l.
2. Process according to claim 1, characterized in that the compound has the general formula:
Figure imgb0015
in which R1, R2, R3, R4, R5, R6, R7, R8 and R9, which can be the same or different, represent a hydrogen atom, an aryl or alkyl radical, a group chosen from among N02, NH2, CF3, CN, OCH3, Cl, F
Figure imgb0016
SCN, OCN,
Figure imgb0017
SR (with R = an aryl or alkyl radical), or a radical chosen from among the alkyl and aryl radicals optionally having one or more substituents chosen in the group including N021 NH2, CF3, SO2, CN, OCH3, Cl, F, SCN, OCN,
Figure imgb0018
SO2R,
Figure imgb0019
SR (in which R is an alkyl or aryl radical).
3. Process according to any one of the claims 1 to 2, characterized in that the concentration of the liquid phase in the compound chosen from among aniline, para-aminodiphenylamine and their derivatives is between 10-3 and 4 mol/l.
4. Process according to any one of the claims 1 to 3, characterized in that the liquid phase containing the super acid and the fluoride ions is the eutectic NH3, HF.
5. Process according to any one of the claims 1 to 4, characterized in that the oxidation is performed chemically.
6. Process according to claim 5, characterized in that the oxidizing agents are chosen from among potassium dichromate, potassium permanganate, osmium tetroxide and ammonium persulphate.
7. Process according to claims 1 to 4, characterized in that the oxidation is performed electrochemically.
8. Process according to claim 7, characterized in that electrodes are used, which are made from a material in the group including platinum, nickel, Monel, carbon and carbon-coated materials.
9. Application of the polyanilines prepared according to the process of any one of the claims 1 to 8 to the production of active materials for use in electrochemical generators.
EP84901780A 1983-05-06 1984-05-04 Process for preparing polyanilines and their applications to electrochemical generators Expired EP0146560B1 (en)

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FR8307958A FR2545494B1 (en) 1983-05-06 1983-05-06 PROCESS FOR THE PREPARATION OF POLYANILINES, POLYANILINES OBTAINED ACCORDING TO THIS PROCESS AND THEIR APPLICATIONS IN THE PRODUCTION OF ELECTROCHEMICAL GENERATORS
FR8307958 1983-05-06

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